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Title: Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity

Abstract

Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orchestrate proton transfer throughout the challenging 4 electron reaction. In order to mimic aspects of this microenvironment, [CoL DMA(CH 3CN) 2][BF 4] 2 (2) was synthesized, where L DMA is a dipyridyldiamine ligand with two dimethylamine bases in the secondary coordination sphere. Structural characterization of the corresponding aqua complexes establish hydrogen bonding between the bound water and pendant base(s). Cyclic voltammetry of [CoL DMA(CH 3CN) 2][BF 4] 2 (2) reveals enhanced oxidative current upon titration with water and controlled potential electrolysis confirms evolution of O 2. The related complex [CoL H(CH 3CN) 2][BF 4] 2 (1), which has the same primary coordination environment as 2 but lacks pendant bases, is inactive. The structural and electrochemical studies illustrate the role positioned proton relays can play in promoting redox reactivity.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of California, Irvine, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1420343
Alternate Identifier(s):
OSTI ID: 1505134
Grant/Contract Number:  
SC0012150; CHE-1338173
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Khosrowabadi Kotyk, Juliet F., Hanna, Caitlin M., Combs, Rebecca L., Ziller, Joseph W., and Yang, Jenny Y. Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity. United States: N. p., 2018. Web. doi:10.1039/c7sc04960a.
Khosrowabadi Kotyk, Juliet F., Hanna, Caitlin M., Combs, Rebecca L., Ziller, Joseph W., & Yang, Jenny Y. Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity. United States. doi:10.1039/c7sc04960a.
Khosrowabadi Kotyk, Juliet F., Hanna, Caitlin M., Combs, Rebecca L., Ziller, Joseph W., and Yang, Jenny Y. Tue . "Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity". United States. doi:10.1039/c7sc04960a.
@article{osti_1420343,
title = {Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity},
author = {Khosrowabadi Kotyk, Juliet F. and Hanna, Caitlin M. and Combs, Rebecca L. and Ziller, Joseph W. and Yang, Jenny Y.},
abstractNote = {Water oxidation is catalysed in Nature by a redox cofactor embedded in a hydrogen-bonded network designed to orchestrate proton transfer throughout the challenging 4 electron reaction. In order to mimic aspects of this microenvironment, [CoLDMA(CH3CN)2][BF4]2 (2) was synthesized, where LDMA is a dipyridyldiamine ligand with two dimethylamine bases in the secondary coordination sphere. Structural characterization of the corresponding aqua complexes establish hydrogen bonding between the bound water and pendant base(s). Cyclic voltammetry of [CoLDMA(CH3CN)2][BF4]2 (2) reveals enhanced oxidative current upon titration with water and controlled potential electrolysis confirms evolution of O2. The related complex [CoLH(CH3CN)2][BF4]2 (1), which has the same primary coordination environment as 2 but lacks pendant bases, is inactive. The structural and electrochemical studies illustrate the role positioned proton relays can play in promoting redox reactivity.},
doi = {10.1039/c7sc04960a},
journal = {Chemical Science},
issn = {2041-6520},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c7sc04960a

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Works referenced in this record:

Electrocatalytic Water Oxidation Beginning with the Cobalt Polyoxometalate [Co4(H2O)2(PW9O34)2]10�: Identification of Heterogeneous CoOx as the Dominant Catalyst
journal, September 2011

  • Stracke, Jordan J.; Finke, Richard G.
  • Journal of the American Chemical Society, Vol. 133, Issue 38, p. 14872-14875
  • DOI: 10.1021/ja205569j

Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
journal, April 2010

  • Chen, Z.; Concepcion, J. J.; Hu, X.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229
  • DOI: 10.1073/pnas.1001132107

Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects
journal, July 2008

  • Sav�ant, Jean-Michel
  • Chemical Reviews, Vol. 108, Issue 7, p. 2348-2378
  • DOI: 10.1021/cr068079z